EP1637210A1 - Verfahren zur Reinigung von Gasen und dazu geeignete Absorptionsflüssigkeit - Google Patents

Verfahren zur Reinigung von Gasen und dazu geeignete Absorptionsflüssigkeit Download PDF

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Publication number
EP1637210A1
EP1637210A1 EP05017819A EP05017819A EP1637210A1 EP 1637210 A1 EP1637210 A1 EP 1637210A1 EP 05017819 A EP05017819 A EP 05017819A EP 05017819 A EP05017819 A EP 05017819A EP 1637210 A1 EP1637210 A1 EP 1637210A1
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EP
European Patent Office
Prior art keywords
gas
alkyl
use according
radical
solvent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP05017819A
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German (de)
English (en)
French (fr)
Inventor
Horst Streitberger
Oliver Dr. Pfüller
Achim Dr. Stankowiak
Alexander Dr. Snell
Norbert Prof. Dr.-Ing. Mollekopf
Hans-Dieter Dr. Müller
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Clariant Produkte Deutschland GmbH
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Clariant Produkte Deutschland GmbH
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Publication date
Application filed by Clariant Produkte Deutschland GmbH filed Critical Clariant Produkte Deutschland GmbH
Publication of EP1637210A1 publication Critical patent/EP1637210A1/de
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1493—Selection of liquid materials for use as absorbents

Definitions

  • the present invention relates to the use of polyalkylene glycol ether amines as the main or minor component of absorption liquids for the removal of contaminating components from gas mixtures of any origin (abbreviated to raw gases).
  • gas mixtures of various origins such as natural gas or synthesis gas, are used to produce hot gases and to produce chemical products.
  • the acid-forming impurities contained in them such as CO 2 , HCl, HCN, H 2 S, SO 2 , COS, CS 2 , lower mercaptans and thioethers are sometimes toxic and harmful to the environment, or they prevent by solid precipitation or poisoning of the catalyst production process. They must therefore be separated from the raw gas. Plant operators are required by law to comply with regulatory requirements that limit sulfur emissions and the emission of other toxic components, and currently the reduction of carbon dioxide emissions is also becoming increasingly important.
  • the most common method of purification is based on absorption, where the good solubility of the contaminating components in certain liquids (detergents) is used for leaching, while the sparingly soluble useful gases remain in the gas stream.
  • the technical implementation of the absorption process is done in a gas scrubber.
  • Their basic structure is determined by the reuse of the detergent by regeneration by the detergent is circulated in such a way that in the actual absorber, the loading of the gases to be washed and carried out in the desorber, the expulsion of the dissolved gases.
  • the desorption is due to the decrease in solubility with increasing temperature or, if the chemical transformations are only partial, with decreasing partial pressure by pressure release or Strip.
  • individual gas components are preferably washed out of the gas mixtures due to different specific physical intermolecular interactions.
  • Characteristic of the physical solubility is that with increasing pressure or partial pressure and kept constant temperature for each individual gas, a specific, approximately uniform increase in the amount dissolved. The solubility of the absorbed components decreases with temperature.
  • the dissolved gas In chemical absorption, the dissolved gas partially or almost completely reacts according to the law of mass action with the solvent or with one component of a solvent mixture, and it is converted into one or more low-volatility substances which remain in the liquid phase.
  • the most common application is chemical absorption in the solution of acid-forming gases in water to which basic additives are added to effectively increase the dissociation of the weakly acidic electrolytes.
  • the dissolution process is based on the fact that the electrolytes, ie the dissolved acidic gases and the basic additives added, partially or almost completely dissociate into ions, the ions having such a strong interaction with the water that they can not leave the liquid phase.
  • an additive in the known methods among others, for example, potash (K 2 CO 3 ), alkanolamines such as mono-, di- or triethanolamine, methyldiethanolamine and diisopropanolamine, or sodium hydroxide used.
  • the base content in these washing solutions is usually between 15 and 60% by weight.
  • the tertiary alkanolamine-containing aqueous solvents form the transition to the combined or hybrid absorbers in which the physical solubility of a basic solvent is increased by mixing with a physical solvent, while reducing the chemical content, for example in mixtures of water, diethanolamine and Methanol (Amisol®).
  • the essential features of the hybrid absorbents are the stronger in the lower partial pressure range and the subsequent increase in the partial pressure noticeable increase in solubility.
  • by the presence of purely physically acting absorbent components in the hybrid detergent and organic sulfur compounds can be washed out, which is only partially possible with purely chemical absorptions.
  • the solubility characteristics determine the scope of application for the various washing processes.
  • Physical washes are used at high process pressures and high concentrations of the gas components to be separated.
  • the regeneration of the detergent can be done by lowering the partial pressure, ie by relaxation or stripping, or by heating.
  • Chemical washes are used at low process pressures or at low concentrations. The degree of purification in the chemical washes is higher than in the physical. For regeneration of the loaded wax, only desorption by "boiling out” can be applied to weakly acidic gases (CO 2 , H 2 S, mercaptans) dissolved in weak bases. In the case of a stronger base or a more strongly basic gas (SO 2 ), the solubility limit for the ion concentration is exceeded and the precipitated salt is discharged. The saturated detergent is returned to the absorption process by being introduced into the unloaded detergent stream which replaces the losses of water with water of crystallization and effluent and the spent active chemical component.
  • weakly acidic gases CO 2 , H 2 S, mercaptans
  • SO 2 more strongly basic gas
  • hybrid washes the advantages of physical and chemical washing are combined so that desorption can also be achieved by lowering the partial pressure by pressure release or stripping; a second stage for fine cleaning is unnecessary.
  • Other advantages include: Due to the presence of purely physically acting absorbent components, organic sulfur compounds are also washed out, which is only possible to a limited extent with purely chemical absorption, and the amount of steam arising in the desorption process is lower than in the case of chemical absorption. As a result, apparatus and energy costs for hybrid washes are lower.
  • the object of the present invention is to search for suitable washing liquids which have a good physical solubility for the acid gases in the pure state and which develop sufficient chemical solubility in the solution in water, so that the effective resulting Solubility of the washing liquid in certain mixing ranges higher than in the conventional combined Solvent mixtures, and a sufficient increase in the solubility is ensured in a large partial pressure range.
  • the detergent must meet the requirements demanded by the technology - high specific solubility and high selectivity of the component to be washed compared to the other gas components, low vapor pressure, easy regenerability, chemical resistance to all raw gas components and oxygen, thermal stability, low procurement costs, permanent availability - Sense of an economical and economical optimal solution.
  • the object of the present invention was to develop a detergent which satisfies the requirements of far-reaching and which is suitable to reduce the investment and operating costs by using smaller apparatus and by reducing energy consumption.
  • the absorption liquid contains one or more polyalkylene glycol amines.
  • R 1 is -CH 2 CH 2 - (OCH 2 CH 2 ) n -OR 3 .
  • R 2 is H.
  • R 3 is methyl.
  • x stands for 1.
  • y stands for 1.
  • z stands for a number between 1 and 4.
  • the polyalkylene glycol ether amines according to the invention are used together with solvents.
  • Preferred solvents are those in which the component A dissolves to at least 0.1 wt .-%, which do not react chemically with the component A, and the have a CO 2 solubility of CO 2 of at least 1.0 Nm 3 per m 3 of solvent at a partial pressure of 1 bar and at 20 ° C.
  • Such solvents are, for example, alcohols, more preferably methanol; Pyrrolidones, particularly preferably N-methylpyrrolidone, N-ethylpyrrolidone, N-propylpyrrolidone and other pyrrolidones having a C 1 to C 12 alkyl radical on the nitrogen; propylene carbonate; 1,3-dimethylpropylene; N-formyl morpholine; Sulfur heterocycles, more preferably sulfolane; Alkanolamines with at least one alkyl radical C 1 to C 6 and at least one C 1 to C 6 alkanol radical, particularly preferably N, N-diethylethanolamine, N, N-dimethylethanolamine, N-methyldiethanolamine, N-methylethanolamine; Amines having at least one C 1 to C 6 -alkanol radical, more preferably monoethanolamine, diethanolamine, triethanolamine, diisopropanolamine; Hydroxyaminoethyl ether
  • the proportion of amines of the formula 1 is from 5 to 99% by weight, in particular from 75 to 98% by weight.
  • Water present in the hybrid laundry is preferably present in amounts up to 15% by weight, especially from 1 to 12% by weight, especially 2 to 10% by weight.
  • the proportion of the solvents is preferably from 1 to 95% by weight, in particular from 2 to 25% by weight.
  • the constituents A and C add up to 100% by weight. In a further preferred embodiment, the constituents A, B and C add up to 100% by weight.
  • the gases to be purified may be any gases containing corresponding impurities and which themselves do not react with the absorption liquid. Particularly suitable is the absorption liquid for the purification of synthesis gas.
  • the impurities to be removed by the use according to the invention are acid-forming and gaseous or vaporous. These are in particular CO 2 , H 2 S, SO 2 , CS 2 , HCN, COS or lower mercaptans with C 1 -C 8 -carbon radicals.
  • the gas scrubbing can be carried out without pressure or under pressures of between 1 and 110 bar, preferably up to 70 bar.
  • the absorption temperature may be 0 to 100 ° C, preferably 10 to 40 ° C.
  • the water vapor contained in the raw gases is also mitentfernt in a wash with the absorption liquids according to the invention, so that a previous dewatering of the raw gas is not necessary.
  • the desorption of water vapor must be carried out accordingly during the regeneration phase.
  • the laden absorption liquids according to the invention should contain as little water as possible, preferably between 0 and 15 mol%, since the solubilities of the gases decrease with increasing water content.
  • a water content of at least 0.5 mol% is necessary for the hydrolysis of COS and CS 2 using a hydrolysis promoter.
  • Another object of the invention is a process for the purification of gases, by bringing the gases at temperatures of 0 to 100 ° C and pressures of 1 to 110 bar in contact with the absorption liquid according to the invention.
  • a synthesis gas produced in a gasification plant was fed into the bottom of the absorption column at a pressure of 50 bar and a temperature of about 30 ° C.
  • the crude gas had the following composition: CO 2 Vol .-% 35.5 H 2 Vol .-% 56.5 CO Vol .-% 8.0
  • PEGDME polyethylene glycol dimethyl ether
  • the target value of the respective test setting is the circulation of the absorption liquid.
  • the absorption liquid according to the invention allows a reduction in the amount of liquid by 42% (experiment 2) or by 55% under these conditions. (Experiment 3).
  • a crude gas produced in a gasification plant was fed under a pressure of 24 bar and a temperature of about 30 ° C in the bottom of the absorption column.
  • the crude gas had the following composition: H 2 S Ppmv 480 CO 2 Vol .-% 20.7 CH 4 Vol .-% 5.6 H 2 Vol .-% 40.7 CO Vol .-% 33.0
  • the H 2 S content could be adjusted via a dosing station.
  • PEGDME polyethylene glycol dimethyl ether
  • the absorption liquid according to the invention allows under these conditions a reduction in the amount of liquid by 23% (experiment 5) or by 36%. (Experiment 6).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Gas Separation By Absorption (AREA)
EP05017819A 2004-09-02 2005-08-17 Verfahren zur Reinigung von Gasen und dazu geeignete Absorptionsflüssigkeit Withdrawn EP1637210A1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102004042418A DE102004042418B4 (de) 2004-09-02 2004-09-02 Absorptionsflüssigkeit, deren Verwendung und Verfahren zum Reinigen von Gasen

Publications (1)

Publication Number Publication Date
EP1637210A1 true EP1637210A1 (de) 2006-03-22

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Family Applications (1)

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EP05017819A Withdrawn EP1637210A1 (de) 2004-09-02 2005-08-17 Verfahren zur Reinigung von Gasen und dazu geeignete Absorptionsflüssigkeit

Country Status (5)

Country Link
US (1) US7387768B2 (enrdf_load_stackoverflow)
EP (1) EP1637210A1 (enrdf_load_stackoverflow)
JP (1) JP5047481B2 (enrdf_load_stackoverflow)
CN (1) CN100525883C (enrdf_load_stackoverflow)
DE (1) DE102004042418B4 (enrdf_load_stackoverflow)

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DE102006010595A1 (de) * 2006-03-06 2007-09-13 Uhde Gmbh Lösungsmittel zur Abtrennung von sauren Gasbestandteilen aus technischen Gasen
DE102007017403B4 (de) * 2007-04-13 2012-05-31 Lurgi Gmbh Verfahren und Vorrichtung zum Herstellen von NH3-Synthesegas
DE102007022168A1 (de) 2007-05-11 2008-11-13 Siemens Ag Verfahren zur Erzeugung motorischer Energie aus fossilen Brennstoffen mit Abführung von reinem Kohlendioxid
DE102008031552A1 (de) * 2008-07-07 2010-01-14 Uhde Gmbh Verfahren zum Entfernen von Sauergasen aus einem Gasstrom
DE102008052612A1 (de) * 2008-10-21 2010-04-22 Uhde Gmbh Waschlösung zur Gaswäsche mit Aminen in wässrige Ammoniaklösung sowie Verwendung
NO332547B1 (no) 2009-07-10 2012-10-22 Statoil Asa Kompakt absorpsjons-desorpsjonsprosess som benytter konsentrert losning
AU2011320717B2 (en) * 2010-10-29 2016-02-04 Huntsman Corporation Hungary ZRt Use of 2-(3-aminopropoxy)ethan-1-ol as an absorbent to remove acidic gases
WO2013003328A1 (en) * 2011-06-28 2013-01-03 Shell Oil Company An ether amine additive impregnated composition useful in the catalytic hydroprocessing of hydrocarbons, a method of making such composition
DE102014107184A1 (de) 2014-05-21 2015-11-26 Technische Universität Dresden Verfahren und Vorrichtung zur Abtrennung von Kohlendioxid aus Gasgemischen
CN105032124A (zh) * 2015-07-03 2015-11-11 南京林业大学 一种醇醚胺类气体净化剂及其应用
CN106422667B (zh) * 2015-08-04 2019-07-30 北京思践通科技发展有限公司 从气体中一步脱除酸性组分和水的方法
CN111770783B (zh) * 2018-02-14 2022-11-29 塔明克私人有限公司 改进的杂质去除方法
JP7713904B2 (ja) * 2022-03-25 2025-07-28 株式会社トクヤマ 二酸化炭素を含むガスから二酸化炭素を分離回収するための吸収液および二酸化炭素の分離回収方法

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GB934636A (en) * 1960-03-04 1963-08-21 Wyandotte Chemicals Corp Process for preparing oxyalkyleneamines
DE2601717A1 (de) * 1976-01-19 1977-07-21 Waichi Tanimura Verfahren zum regenerieren organischer loesungsmittel
DE19540091A1 (de) * 1995-10-27 1997-04-30 Basf Ag Verwendung von Fettsäurederivaten als Tenside
US6277345B1 (en) * 1998-11-25 2001-08-21 Clariant Gmbh Process for the purification of gases
DE10217469C1 (de) * 2002-04-19 2003-09-25 Clariant Gmbh Verfahren zur Entschwefelung von Produkten der Rohölfraktionierung

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GB934636A (en) * 1960-03-04 1963-08-21 Wyandotte Chemicals Corp Process for preparing oxyalkyleneamines
DE2601717A1 (de) * 1976-01-19 1977-07-21 Waichi Tanimura Verfahren zum regenerieren organischer loesungsmittel
DE19540091A1 (de) * 1995-10-27 1997-04-30 Basf Ag Verwendung von Fettsäurederivaten als Tenside
US6277345B1 (en) * 1998-11-25 2001-08-21 Clariant Gmbh Process for the purification of gases
DE10217469C1 (de) * 2002-04-19 2003-09-25 Clariant Gmbh Verfahren zur Entschwefelung von Produkten der Rohölfraktionierung

Also Published As

Publication number Publication date
CN1748840A (zh) 2006-03-22
DE102004042418B4 (de) 2008-04-30
US7387768B2 (en) 2008-06-17
DE102004042418A1 (de) 2006-03-23
JP5047481B2 (ja) 2012-10-10
CN100525883C (zh) 2009-08-12
US20060045830A1 (en) 2006-03-02
JP2006068740A (ja) 2006-03-16

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